CA1099704A - Dyes, processes for their production and use thereof - Google Patents

Abstract

Abstract of the Disclosure Dyes of the formula

Description

9~

The present invention provides dyes of the formula - ;
~,N~ ~ ~1), W
R N N R~
X
~ .' ..
. .
wherein D is the radical of an organic ~ye, Rl is hydrogen or methyl, R2 is alkyl of 2. to 4 carbon atoms, and ~ is hydrogen or methyl.
In the dyes of the formula (1), the radical D
is in particular the radical of a dye of the monoazo, poly-azo, metal complex, anthraquinone, phthalocyanine, forma-zane, azomethine, nitroaryl, dioxazine, phenazine or stilbene series.
The radical D preferably contains water-solubilising groups, in particular sulphonic acid groups.
Preferred dyes are those of the formula I where-in D is the radical of an azo.dye.
Particularly preferred dyes are those of the ~ormula , . :.

7~4L

~10 A-N=N _ 1~ ~ (5O3H)m (2) ~ ~ } N~l- ~ C ~ C N ~

~ C / X

wherein A is a benzene or naphthalene radical, m is 1 or 2, n is 0 or 1, p is O or 1, R is alkyl of 2 to 4 carbon atcms, and X is h~drogen or methyl, and the kenzene or naphthalene radical A and the kenzene radical B can contain further substituents.
The substituent R2 in formMla (1) as alkyl of 2 to 4 carbon atoms is ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl.
The radical of an organic dye D in formula (1), and the benzene or naphthalene radical A and the benzene radical B in form~la (2) can contain further sukstituents, for example: alkyl groups of 1 to 4 carbon atcms, such as methyl, et~yl and pLopyl; alkoxy groups of 1 to 4 carkon atcms, such as methoxy, ethoxy, propyloxy and isopropyloxy, acylamino groups of 1 to 6 carbon atoms, such as acetylamino, propionylamlno and kenzoylamino; amino groups, such as -NH2, methylamino and eth~lamino; the ureido, hydroxyl and carkoxyl gro~; and halogen, such as fluorine, chlorine and bromine.
The radicals D, A and B contain in particular sulfonic acid groups as substituents.
If the radical D or A contains complex-forming groups, such as hydro-xyl, carboxyl, amino and sulfo groups, it is also possible to obtain the heavy metal canplexes of the dyes of the formulae (1) and (2).
Valuable dyes of the formula (1) are for example the aye of the formula ~.
, ', - ` ;: :: :

HO
H3CO - ~ N - N ~ ~ NH - C~ \C N - ~ ~3) .... -- ~C

and the dye of the formula HO NH - CO ~ NH Cf~N~c N ~
~ ~ = N ) ~ N ~N ~2Hs (43.

- S03H ~03S S03H "
, -- . . . . .. , . , . _ _ , _ .. _ , Th~ dyes of the formula (1) are fibre-reactive as they contain a removable fluorine atom in the s-triazine radical.
By fibre-reactive compounds are meant those com-pounds which are able to react with the hydroxyl groups of cellulose or with the amino groups of natural or synthetic polyamides to form covalent chemical bonds.
The dyes of the formula (1) are obtained by con-densingg in any order, 2,4,6-trifluoro-s-triazine of the formula - F - C~ C - F (5), N N
~C~
F

an organic dye of the formula - NH - . ~6)~
R

, ..
, .

. ~, 9 7 ~ ~

or a primary product o~ an organic dye of the formula (6), and an aminobenzene of the formula HN ~ (7) X . ...~
to give a dye of the formula (1), and, if primary products are used, converting these latter in~o the desired end dyes of the formula ~1).
A preferred embodiment of the process for the production of the dyes of the formula (1) consists in using as starting materials organic dyes of the formula (6), wherein D is the radical of an azo dye, or in condensing diazo components and/or coupling components which contain a N(Rl)H group with the 2,4,6-trifluoro s-triazine of the formula (6), and subsequently, or after the further conden-sation with the aminobenzene of the formula (7), finally obtaining the ènd dye by coupling with the respective other component of the azo dye.
The preferred dyes of the formula (2) are ob-tained by reacting, in any order, a diazotised amino com-pound of the formula - NH~ (8) a coupling component of the formul.a HO .
' '' ' ~ ~ - - .

NH~Co3~3}-NH~H (9)

2~4,6 trifluoro 1,3,5 t~iazine ox the formula - . .. -- . . ~
, F
",C
I "
F ~ C C - F
~ N' and an aminobenzene of the formuLa }1~ 10~
~, . .

by coupling and condensation, to give a dye of the formula (2) o If the dyes of the formula (1) or (2) contain complex-forming groups, they can subsequently be reacted with heavy metal donors.
As the individual process steps described above can be carried out in varying sequence, and if desired also in ~ome casessimultaneously, different variant of the process are possibleO
In general, the reaction is carried out stepwise in succession and the sequence of the simple reactions between the individual reaction components of the formulae (5)~ (6) and ~7) can be freely chosen.
Important process variants for producing the preferred dyes of the formula (2) comprise:
1) coupli.ng a diazotised amino compound of the formula (8) with a coupling component of the formula (9) to-~ive an azo compound of the formula HO
A-N=N~ (S03H)m ~H~(-CO) p ~3 -NH~H

:. ~
~ - ~

997¢J ~L

condensing this azo compound with 294~6-~rifluoro-1,3,5 triazine of the formula (5) and condensi.ng the primary condensation product with an aminobenzene of ~he formula (10) to give an azo dye of the formula (2);
~3 condensing a coupling component of the formula ~9) with 2,4,6-~rifluoro-1,3,5-triazine of the formula (5), condensing the primary condensation procluct with arl amino-benzene of the formula (10) and coupling the secondary condensation product with a diazotised amino compound of the formula (8) to give an azo dye of the formula (2);

3) condensing a coupling component of the formula (9) with 2,4,6-trifluoro-1,3~5-triazine of the formula (5)~ coupling a diazotised amino compound of the formula (8) to the primary condensation product, and condensing the resulting azo compound with an aminobenzene of the formula (10) to give an azo dye of the formula ~2).
The particularly valuable dyes of the formulae (3~ and (4) are preferably obtained by process variant 1) by condensing 2~amino-6-(4'-methoxy-2' sulfophenylazo)-5-hydroxynaphthalene-7-sulfonic acid with 2,4,6-trifluoro-s-triazine and replacing a fluorine atom at the s-triazine ring by a N-ethylphenylamino group by condensation with N-ethylaminobenzene, or 'by condensing 1-(4' aminobenzoyl-amino)-7-(2"-sulfophenylazo)-8-hydroxynaphthalene-3,6-disulfonic acid with 2,4,6-trifluoro-s-triazine and re-p'Lacing a fluorine atom at the~s-triazine ring by a N-ethylphenylamino group by condensation with N-ethylamino-benzene.
As dyes of the form-lla (6) there are used in particular those wherein the radical D is the radical of a dye of the monoazo, polyazo, metal complex, anthraquinone, 7~L

phthalocyanine, formazane, azomethine, nitroaryl, dioxazine, phenazine or stilbene series.
Preerably, organic dyes of the formula (6), wherein the radical D contains water-so:Lubilising groups, or primary products of organic dyes of the formula (6) which contain water-solubilising groups, are used as starting materials. Suitable water-solubilising groups are in particular sulphonic acid groups.
The preferred starting materials are organic dyes of the formula (6), wherein D is the radical of monoazo or disazo dye Such a preferred embodiment comprises condensing?
in any order? an organic dye of the formula K - N = N - Dl - NH (12) Rl wherein Dl is the radical of a diazo component of the benzene or naphthalene series, K is the radical of a coup ling component of the benzene, naphthalene or heterocyclic series, and Rl is hydrogen or methyl, 2,4,6-trifluoro-s-triazine of the formula (5) and an aminobenzene of the formula (7), to give a dye of the formula (1).
In a modification of the above process, the dyes of the formula (1), wherein D is the radical of an organic dye composed of two or more components, can be obtained by condensing a component of the dye of the formula (6) which contains a -~N group, a 2,4,6-trifluoro-s triazine of the formula (5) and an aminobenzene of the formula (7), and, in any step of the process, reacting the condensation pro-duct with the other component or components of the dye of the formula (6) to give a dye of the formula ~1).

, : . ~
..", : :.. " ~
. .

~9 ~ 8 Examples of such organic dyes wh;ch are composed of two or more components are: monoazo~ disazo, trisazo, tetra20, metal complex, formazane and aæomethine dyes~
The above described process modification is chiefly of importance for the production of dyes cf the formula (1), wherein the radical D is the radical of an azo dye which contains sulfo groups. In these dyes, that portion of the azo dyestuff radical to which the s-triazine is attached can be either the radical of the diazo compo-nent or the radical of the coupling component. This possi-bility gives rise to two variants of the above described modification of the process~
The first of these two variants consists in con-densing a diazo component which contains a -NH group with - Rl 2,4,6-trifluoro-s-triazine of the formula (5), diazotising the resulting condensation product and coupling the diazo-nium compound to a coupling eomponent, and reacting the resulting azo compound, before or a~ter the coupling, with an aminobenzene of the formula ~7).
The second variant consists in condensing a coupling component which contains a ~i group with 2,4,6-Rl trifluoro~s-triazine of the formula (~ and coupling a diazotised diazo component to the condensation product and reacting the resulting azo compound, before or after the coupling~ with ~n aminobenzene of the for~ul~ (7).
In this process variant9 it is possible to obtain dyes of the formula (1) which contain two reactive radicals by condensing a diazo component which contains a -NH group Rl ,, .-; ~ , ,, -, . :
. ~ , . ..
:, , ~ ~9 ~ 7~ ~

with a 2,4~6-trifluoro s triazine o:f the formula ~5), and also condensing a coupling component whi.ch contains a -~1 group with a 2,4,6-trifluoro-s-triazine of the formula (5) and diazotising the condensation product of the diazo com-ponent and coupling the diazonium compo~md to the conden-sation product of the coupl;ng component and reacting the resulting azo compound, before or after the coupling, with an aminobenzene.
Dyes~ which contain two or more reactive radicals can also be obtained by condensing dyes of the formula (6) which contain further ~NH groups in the radical D with a R

corresponding amount of the 2,4,6-trifluoro-s-triazine of the formula (S), so that two or more s-triazine radicals are introduced into ~he dye moleculeO
The condensation of the 2,4,6-trifluoro~s-triazine of the formula (5) with the organic dyes of the formula (6), the dia20tisable and/or couplable components which contain a NH group, and with the aminobenzenes of the formula (7), Rl is carried out preferably in aqueou~ solution or suspension, at low temperature and at a weakly acid, or neutral to weakly alkaline pH value, and s~uch that at least one re-movable fluorine atom remains in the end dye of the formu-la (1). The hydrogen fluoride which is set free during the condensation is advantageously neutralised continuously by the addition of an aqueous alkali hydroxide~ carbonate or bicarbonate.
As starting materials for the production of the dyes of the formula (1) there may be mentioned:

.. .~
: ' ' ' `~

7~

- ~o -a) 2,4,6-trifluoro-s-triazine (cyanuric fluoride) o the formula (5) b) Organic d~es of thc formula C6) 0i1 ~1 - N = N ~ ~
HO3S ~ ~1 (13) wherein Dl is an at most bicyclic aryl radical which contains no azo groups and -NHRlgroups, R is hydrogen or methyl and the-NHR group is preferably bonded to the 5-, 6-, 7- or 8-position of the naphthalene nucleus, and which additionally can contain a sulfonic acid group in the 5-or 6-position of the naphthalene nucleus.
Dl can be a radical of the naphthalene or benzene series which does not containany azo substituents, or can be a stilbene, diphenyl, benzthiazolylphenyl or di-phenylamino radical. In this class, attention is also drawn to the related dyes in which the -NHRl group, instead of being bonded to the naphthalene nucleus, is bonded to a benzoylamino or anilino group which is bonded to the 5-, -~
6-~ 7- or 8-position of the naphthalene nucleus.
Particularly valuable starting dyes are those r wherein Dl is a sulfonated phenyl or naphthyl radical, especially those which contain a -SO3H group in the ortho-position to the azo bond. The phenyl radical can be fu~ther substituted, for example by halogen atoms, such as chlorine atoms~ alkyl radicals, such as methyl, acylamino groups, such as acetylamino and alkoxy radicals, such as methoxy~
2r Disazo compounds of the formula ~13), wherein Dl is a radical of the azobenzene, azonaphthalene or phenylazonaphthalene series and the naphthalene nucleus is substituted by the -~HRl group and, if desired, by sulfo-nic acid~ as in class 1.

' ' ' .

. . .

3. Monoazo compounds of the forrnula D~ - N - N ~- ~ - NHRl (14) wherein Dl is an at most bicyclic aryl radical, as des-cribed in class 1~ and is preferably a disulonaphthyl radi .
cal or a stilbene radical, R is hydrogen or methyl, and the benzene nucleus can contain further substituents$ such as halogen atoms or alkyl, alkoxy, carboxylic acid, ureido and acylamino groups.

4. Monoazo or disaæo compounds of the formula H ~ Dl N N K (15), Rl wherein Dl is an arylene radical, ~or example a radical of the azobenzene, azonaphthalene or phenylazonaphthalene series or, preferably, an at most bicyclic arylene radical of the benzene or naphthalene series and K is the radical of a naphtholsulfonic acid or the radical of an enolised or enolisable ketomethylene compound (such as an acetoace-tarylide or a 5-pyrazolone) with the OH group in the ortho-position to the azo group, and R is hydrogen or methyl. Dl represents preferably a radical of the benzene series which contains a sulfonic acid group.

5. Monoazo or disazo compounds of the formula Dl-N=N-K -NHR (16), wherein Dl is a radical of the types defined for Dl in classes 1 and 2 above and Kl is the radical of an enolisab-le ketomethylene compound (such as an acetoace~arylide or a S-pyrazolone) with the OH group in the ortho-position to the azo group

6~ lhe metal complex compounds, for example the copper complexes, chromium complexes and cobalt complexes, , - ; .

of the dyes of the form~llae (13) to (16), wherein each of ls K and Kl has the indicated meaning, and f~thermore a metallisable group (for example a hydroxyl, lower alkoxy or earboxylic acid group) is present in the ortho-position to the azo group in Dl.
~ .
Class 1:
6-amino-1-hydroxy-2-(2'-sulfophenylazo~-naphthal-ene-3-sulfonic acid, 6-methylamino-1-hydroxy-2-(4'-accetyl-amino-2'-sulfophenylazo)-naphthalene-3-sulfonic acid, 8-amino-1-hydroxy-2-(2'-sulfophenylazo) naphthalene-3,6-di-sulfonic aeid, 8 amino-1-hydroxy-2-(4!-chloro-2'-sulfo-phenylazo)-naphthalene-395-disulfonic acid, ;~

7-amino-2-~2',5'-disulfophenylazo)-1-hydroxynaphthalene-3-sulfonic acid, 7-methylamino-2-(2'-sulfophenylazo)-1-hydroxynaphthalene-3-sulfonic acid, 7-methylamino-2-(4'-methoxy-2'sulfophenylazo)-1-hydroxy-naphthalene-3-sulfonic acid, 3-(3'-aminobenzoylamino)-l~hydroxy~2-(2'-sulfophenylazo)-naphthalene-3,6-disulfonic acid,

8-amino-1-hydroxy-2,2'-azonaphthalene 1',3',5',6-tetrasul-fonic acid, 8-amino-1-hydroxy-2,2' azonaphthalene-1',3',5'-trisulfonic acid, 6-amino 1-hydroxy-2,2'-azonaphthalene-1',3,5'-trisulfonic acid, 6-methylamino-1-hydroxy-2~2' azonaphthalene-1',3,5'-trisul~
fonic acid~
7-amino-1-hydroxy-2,2'-azonaphthalene-1',3-disulfonic acid, 8-amino-1-hydroxy~2-(4'-hydroxy-3'-carboxyphenylazo)~
naphthalene-3,6-disulfonic acid and 6-amino-1-hydroxy-2-(4'-hydroxy-3'-carboxyphenylazo)-naph-thalene-3,5-disulfonic acid~

` ~ , ~ 39g 7~4 Class 2:
8-amino-l~hydroxy-2-[~ (2"-sulfophenylazo) 2'-methoxy-5'-methylphenylaæo]-naphthalene-3,6-di.sulonic acid, 8-amino-1-hydroxy-2-[4'-(4"-methoxyphenylazo)-2'-carboxy-phenylazo]-naphthalene-3,6-disulfonic acid, 8-amino-1-hydroxy-2~[4'-(2"-hydroxy-3",6"-disulfo l"-naph-thylazo)-2'-carboxyphenylazo]-naphthalene-3 9 6-disulfonic acid, 4,4'-bis-(8"-amino-1"-hydroxy-3"~6"-disulfo-2"-naphthylazo)-3,3'-diemthoxydiphenyl and 6-amino-1-hydroxy-2-[4'-(2"-sulfophenylazo)-2'~methoxy-5'-methylphenylazo]-naphthalene-3~5-disulfonic acid Class 3:
2-(4'-amino-2'-methylphenylazo)-naphthalene-4,8-disulonic acid, 2-(4'-amino-2'-acetylaminophenylazo)-naphthalene-5,7-disul-fonic acid, 4-nitro-4'-(4"-methylaminophenylazo)-stilbene-2,2'-disul-fonic acid, 4-nitro-4'-~4"-amino-2"-methyl-5"-methoxy-phelylazo)-stil-bene-2,2'-disulfonic acid, 4-amino-4'-(4i'-methoxyphenylazo)-stilbene-2,2'-disulfonic acid, and 4-amino-2-methylazobenzene-2',5'-disulfonic acid Class 4: ~
1-~21,5'-dichloro-4'-sulfophenyl?-3~methyl-4-(3"-amino-4"-sulfophenylazo)-5-pyrazolone, l-~4'-sulfophenyl)-3-carboxy-4-(41amino~3"-sulfophenylazo)-5-pyrazolone, ..
`:. ' ' ' ' '7~

1-(2'-methyl-5'-sulfophenyl)-3-methyl-4-(4"-amino3"-sulfo-phenylazo)-S~pyrazol.one, 1-t2'-sul:Eophenyl)-3-methyl-4-~3"-amino-4"-sul:Eophenylazo~-5-pyrazolone, 4-amino~ (3"-methyl-1"-phenyl-4"-pyrazol-5"-onylazo)-stilbene-2,2' disulfonic acid~
4-amino-4'-(2"-hydroxy 3",6"-disulfo-1"-naphthylazo)-stilbene-2,2'-disulfonic acid, 8-acetylamino-1-hydroxy-2-(3'-amino-4'-sul:Eophenylazo~
naphthalene-3,6-disulfonic acid, 7-(3'-sulfophenylamino3-1-hydroxy-2-(4'~amino-2'-carboxy-phenylazo)-naphthalene-3-sulfonic acid, 8-phenylamino-1-hydroxy 2-(4"-amino-2'-sulfophenylazo)-naphthalene-3,6-disulfonic acid and 6-acetylamino-1-hydroxy-2-~5'-amino-2'-sulfophenylazo)-naphthalene-3-sulfonic acid.
Class 5:
1-(3'~aminophenyl)-3-inethyl-4-(2',5'-disulfophenyl-azo)-.
5-pyrazolone, 1-(3'-aminophenyl)-3-carboxy-4-(2'-carboxy-4'-sulfophenyl-azo)-S-pyrazolone, 4-amino-4'-[3"-methyl-4l'-(2"',5"'-disulfophenylazo)-1"-pyrazol-5"-onyl]-stilbene-292'-disulfonic acid and 1-(3'-aminophenyl)-3-carboxy-4-~4"-(2"' 3 5il'-disulfophenyl-azo)-2"-methoxy-5"-methylphenyla20]-5-pyrazolone.
Class 6: ~
The copper complex of 8-amino-1-hydroxy 2-(2'-hydroxy-5"-sulfophenyla~o?-naphthalene-3,6-disulfonic acid, the copper complex of 6-amino-1-hydroxy-2-(2'~hydroxy-5'-sulfophenylazo)-naphthalene-3-sulfonic acid, the copper complex of 6 amino-l~hydroxy-2-(2'-hydro~y-5'-sulfophenylazo~-naphthalene-3,5-disulfonic acid, 7~a ~- 15 -~he copper complex of 8-amino-1-nydroxy-2 (2'hydroxy-3'-chloro-5'-sulfophenylazo)-naphthalene-3, 6-disulfonic acid, the copper complex of 6-methylamino-1-hydroxy-2~(2'-carboxy 5'-sul.~ophenylazo)-naphthalene-3-sul~on.ic acid, the copper complex of 8-amino-1-hydroxy--2-[4'-(2"-sulfo-phenylazo)-2'-methoxy-5'-methylphenylazo~-naphthalene-3, 6-disulfonic acid, the copper complex of 6-amino-1-hydroxy-2-~4'-(2", 5"-di-sulfophenylazo)-2'-methoxy-5'-methylphenylazo]-naphthalene-3,5-disulfonic acid, the copper .complex of 1-(3l-amino-4' sulfophenyl)-3-methyl-4-~4"-(2"'-5"'-disulfophenylazo)-2'l-methoxy-5"-methyl-- phenylazo]-S-pyrazolone, the copper complex of 7-(4'~amino-3'-sulfoanilino)-1-hydroxy-2-[4"-(2"', 5"'-disulfophenylazo)-2"-methoxy-5"-methylphenylazo]-naphthalene-3-sulfonic ac;d, the copper complex of 6-(4'-amino-3'-sulfoanilino)-1-hydroxy-2-(2"-carboxyphenylazo)-naphthalene-3-sulfonic acid, the 1,2-chromium complex of 7-amino-6'-nitro 1,2'-dihydroxy -2, 1 1azonaphthalene-3, 4-disulfonic acid~
the 1~2-chromium complex of 6-amino-1-hydroxy-2-(2'-corboxy-phenylazo)-naphthalene-3-sulfonic acid, the 1,2-chromium complex of 8-amino-1-hydroxy-2-(4'-nitro-2'-hydroxyphenylazo)-naphthalene-3, 6-disulfonic acid, the.ll2 cobalt complex of 6- (4'-amino-3'-sulfoanilino)-l-hydroxy-2 (5"-chloro-2'-hydroxyphenylazo)-naphthalene-3-sulfonic acid, the lS2-chromium complex of 1-(3'-amino-4'-sulfophenyl)-3-methyl-4-(2"-hydroxy-4" sulfo-1"-naphthylazo)-5-pyrazo-lone, .
.- .

1~9!7~

1~ -the 192--chromium complex of 7-(4'-sul~oanilino)-1-hydroxy-- 2-(4''-amino-2''-caxboxyphenylazo)-naphthcllene-3-sulonic acid and the 1,2-chromium complex of 1-(3'-aminophenyl)-3-methyl-4-(4"-nitro-2"-carboxyphenylazo)-5-pyrazolone.
Particularly important azo dyes which can be used for the production of the dyes of the'formula (1) are the azo dyes of the formulae ~S031~)o-3 .. ~ ~N=N ~ K
., ,- ,' ~17) . ' '.
I~ .

, H; OCH3; ~H-acyl t l . , OH N-ll (H3S)0_3 ~ ~ N;N ~ ~ ~ _ ~SO~}~)l-3 , (18) H; ~3; OC~3; lyH-Qcyl N - H

(HO3S)I ~ ~ N=~ _ ~ ~ (S3H)0 3 . . - C~.3; NH-a ';
wherein K is the radical of a coupling component of the benæene, naphthalene or heterocyclic seriesa acyl is a low molecular aliphatic acyl radical of not more than 3 carbon atoms or an aromatic radical of not more than 8 ~ ' -~399'7~L

carbon atoms and Rl is as de~ined in formula (1)~ and the metal complex azo dyes of the formulae ~ ~ Me ---- N--H

(H035) N=N ~ (S03l~ 3 H;01l;~0~ ~ (20) ~l; cl ; ~û2 ..
.

. (S03II?o 2 .-. .
~O ---~u --- O
N~12 (or NH-acyl) ( 03~ 3 , ~
NH
R

wherein R and acyl are as defined in the formulae (17), (18) and ~19) and Me represents Cu, Cr or Co.
7. Anthraquinone compounds which contain a group of the formula -NHRl~ wherein R is hydrogen or methyl, bonded to an alkylamino or arylamino group, which is itself bonded to the ~-position of the anthraquinone nucleus, in parti-cular of the formula N~R

-S03~I

NH--Z '~NIlR

- : .

, ~
~ . . .
.

~os~a~ ,.

wherein the antraquinone nucleus ean contain an additional sulphonic acid group in the S-, 6-, 7- or 8 position and Z' isa bridgemember which is preferably a divalent radi-cal of the benzene series, for example a phenylene, di-phenylene or 4,4'-stilbene or azo'benzene radical. Pre ferably Z' should contain one sulfonic acid group for each benzene ring present.
Exam~les l-amino-4-(4'-aminoalilino~anthraquinone-2,3' disulfonic acid and the corresponding 2,3',5-,2,3',6 and 2,3',7-tri su'l-~onic acids, 'l-amino-4-(4l-amino-4'-benzoylam'noanilln~)~
anthraquinone-2,3'-disulphonic acid and the corresponding 2,3'5-trisulfonic acid, 1-amino-4-[4'-(4"-aminophenylazo)-anilino]~nthraquinone-2,2",5-trisulfonic acid, l-amino-4-(4'-amino-3'-carboxyanilino~nthraquinone-2,5-disulfonic acid, l-amino~4-(3'-aminoanilino~nthraquinone-2,4',5-tri-sulfonic acid and the corresponding 2,4-disulfonic acid, l-amino-4-['-(4"-aminophenyl)-anilino]-anthraquinone-2,3", 5-trisulfonic acid, 1-amino-4-(4l-methylamino)-anilino-anthraquinone~3' disulfonic acid and the corresponding 2,33,5-trisulfonic acid, 1-amino-4-(4'-n-butylamino)-anilinoanthraquinone-2,3'-disulfoni~ acid, 1-amino-4-(4'-methylarnino-3'-carbocyanilino~anthraquinone-2-sulfonic acid, l-amino-4-(3l-~-hydroxyethylamino)-anilinoanthraqui none-2,5-disulfonic acid, 1 (4'-aminoanilino)-anthraqui-none-233'-disulfonic aeid and 1-amino-4 (4'-amino-2'-methoxyanilino)-anthraquinone-2,3'-disulfonic acid 8. Ph~haloeyanine compounds of the formula .

Pc ~ (S~2- ~)n (23) ~ (S02NH~ m .

.-.

~9~

wherein Pc denotes a phthalocyanine nucLeus, preferablycopper phthalocyalline,~ is ~OH and/or -NH2, Z' i.s a bridge member, preferably an aliphatic, cycloa:Liphatic or aroma-tic bridge, and each of n and m is 1, 2 or 3 and can be identical or diferent, provided tha~ the sum of n + m is no t greater than 4.
The dye compounds of the phthalocyanine series which can be used as starting materials in the process of the invention are preperably metal-containing phthalocya-nines, such as copper phthalocyanlnes, ~hich contain at least one water-s~lubilising group, such as a sulfonic acid group, and at least one group of the formula -NHRl, wherein Rl is a hydrogen atom or an alkyl group. The -NHRl group or groups can be bonded direct or through a divalent bridge to the benzene rings of the phthalocyanine nucleus, for example through a -phenylene-g -CO-phenylene-, -SO2-phenylene-, -NH-phenylene-, -S-phenylene-, O-phenylene-, -CH2S-phenylene-, -CH20 phenylene-, -CH2-phenylene-~-SCH2-phenylene-, -S02CH2-phenylene-, -SO2NRl-phenylene-, -CH2-, -SO2NRl-arylene, -NRlCO-phenylene-, -NRlSO2-pheny lene~, -SO20-phenylene-, -CH2-, -CH2NRl-phenylene-, -CH2NH-CO-phenylene-, -SO2NRl-alkylene-, -CH2MRl alkylene-, -CONRl--ylel, e- -CO~ arylerle =, =Sv2 above divalent bridge members, Rl is a hydrogen atom, an alkyl or cycloalkyl group, arylene denotes a divalent aro-matic radical which is unsubstituted or substitu-ded, for example by halogen atoms, alkyl or alkoxy groups, and where-in the terminal bonds may be attached to identical or different nuclei, and alkylene denotes a divalent alipha-tic radical which can include heteroatoms, such as nitrogen, in the chain of atoms, for example the radical -CH2CH2-NH-CH2 CH2 - .
As examples for such divalent aromatic radicals, which are referred to as arylene, there may be mentioned:

.

7~

~o -aromatic nucle.i, for example a benzene~ naphthalene~acridine and carbazole nucleus, which can carry further substituents, and radicals of the formula ~ D ~ / (24) wherein the benzene rings can carry further substi~uents and -D- clenotes a bridging group, for example -CH=CH-, -NH-~ -S-, -O-, -S02-, -NO-N~, -N=N-, -NH-CO-NH-CO-NH-, -O-CH2CH20- or - ~ N
Il 1l `(25) ~0/ ,, ' Exa~ples 3-(3'-amino-4'-sulfopheny].)-sulfamyl~copper phthalocyanine-tri-3-sulfonic acid, di-4-(3'-amino-4'-sulfophenyl~-sulfamyl-copper phthalo-cyanine-di-4-sulfonic acid, 3-(3'-aminophenylsulfamyl)-3-sulfamyl-copper phthalocya-nine-di-3-sulfonic acid, copper phthalocyanine-4-N-(4-amino-3-sulfophenyl)-sulfon-amide-4',4",4"'-trisulfonic acid, cobalt phthalocyanine-4-4'-di-N-(4'-amino-4'~sulfophenyl)-carboxamide-4",4"'-dicarboxylic acidS and copper-4-~4'-amino-3'-sulfobenzoyl) phthalocyanine.
Mixtures of phthalocyanines can also be used. For example, a mixture of approximately equal parts of copper phthalo-cyanine-N-(4 amino-3-sulfophenyl)-sulfonamide-trisulfonic acid and copper ph~halocyanine-di-N-(4-amino-3-sulfophenyl)-sulfonamide-disu~fonic~ acid can be used.

. , -- ~

9. Nitro dyes of the Eormula z 02N-D-N-Q (26), wherein D is a naphthalene or benzene nucleus which can be further substituted, the nitrogen atom N is in the ortho-position to the nitro group, Z is a hydrogen atom or an unsubstituted or substituted hydrocarbon radical and Q is a hydrogen atom or an organic radical bonded to the nitro-gen through a carbon atom, and wherein Q and Z are not both hydrogen atoms, and Q can be bonded to Z, if Z is a hydro-carbon radical, or can be bonded to D in the ortho-position to the nitrogen atom N to form a heterocyclic ring, and which contain at least one group of the formula ~NXRl~
wherein Rl is hydrogen or methyl, in particular nitro dyes of the formula - ~- NH-B-NHRl (27)~
~ 2 wherein V and B are monocyclic aryl nuclei and the nitro group in V is the ortho-position ~o the NH group.
Exam~e 4-Amino-2'nitro-diphenylamine-3,4' diswlfonic acid.
9. Metal complexes of formazane dyes of the formula N=N-A~Y ~1 Q-CH _ -NH (n = 1 or 2) (24) B-Y2 ~ _ ,:, .. .. ..

wherein Q is an organic radical, a nitro or cyano group, A and B are radicals of diazo components of the benzene, naphthalene or heterocyclic series and each of Yl and Y2 is a substituent which is bound in the ortho-position to the azo group and which is able to form a complex with a heavy metal, and R has the indicated meaning. The radical Q is especially a ractical of the benzene series~ such as phenyl or sulfophenyl, or a low molecular alkyl group, such as a methyl group, a low molecular alkanoyl group, a low molecular, preferably Cl-C4-carbalkoxy group, a benzoyl group or a heterocyclic radical, and A and B are preferably phenyl radicals which are substituted by sulfo, sulfonamido or alkylsulfonyl groups. Suitable substituents Yl and Y2 are above all the hydroxyl and carboxyl groups.
Suitable heavy metals are copper, chromium, cobalt and nickel.

the copper complex of 2'-carb~xy-2"-hydroxy-3"-amino-1,3,5 triphenylformazane-4',5",3"'-trisulfonic acid, the copper complex of 2',2"-dihydroxy-3'-amino-5'-methyl~
sulfonyl-1.3,5-triphenyl-3",5",4"'-trisulfonic acid, the copper complex of 2'~carboxy-4'-amino-2" hydroxy-1,3, S-triphenylformazane-3",5t',2l"-trisulfonic acidg the copper complex of 2'-hydroxy-2"-carboxy-4"l-amino-1,3, 5-triphenylformazane-4'-4"-disulfonic acid, the copper complex of 2',21'-dihydroxy-51'-amino-1,5-diphenyl-3-me~hylformazane-5',3"-disulfonic acid, the copper complex of 2',2"-dihydroxy-5'-amino-1,3,5-tri-phenylformazane-3'-3",5"-trisulfonic acid, ~' the copper complex of 2' carboxy-3'-amino-2'l-hydroxy-3"' (l""-phenyl_31111-methyl-pyra~ol-5l1~l-onyl-4~ -azo)-l~3~5 trophenylformazane-3",5'~,2"",5""-tetrasulfonic acid '` ' .: : ' '~ ' ' ~"~' ,, '~; ' ' ` ~ . . .

- ~3 -the nickel complex of 2'12"-dicarboxy~ 5-diphenyl-3-(m-aminobenzoyl)-formazane-4',4"-disulfonic acid.
c) minobenzenes of the formula (~
N-ethylaminobenzene N-propylaminobenzene, N-n-butylaminobenzene, 3-ethylaminobenzene, 3-n-butylaminobenzene, 2-ethylamino-1-methylbenzene.
Examples of starting materials which can be used in the production of the preferred dyes of the formula (2) are:
D.iazotisableam~no compo~mds of the formula-(8) ~diazo components) l-aminebenzene-2-, -3- and -4-sulfonic acid, l-aminobenzene-2,4- and -2,5-disulfonic acid, l-amino-4-methylbenzene-2-sulfonic acid, l-amino-3-methylbenzene-6-sulfonic acid, l-amino-6-methylbenzene-3- or -4-sulfonic acid, l-amino-2,4-dimethylbenzene-6-sulfonic acid, l-amino-2-carboxybenzene-4-sulfonic acid, l-amino-4-carboxybenzene-2~sulfonic acid~
l-amino-4- or -5-chlorbenzene-2-sulfonic acid, l-amino-6-chlorobenzene~3- or -4-sulfonic acid, l-amino-3,4-dichlorobenzene-5-sulfonic acid, l-amino,2,5-dichlorobenzene-4-sulfonic acid, l-amino~4-methyl-5-chlorobenzene-2-sulfonic acid, l-amino-5-methyl-4-chlorobenzene-2-sulfonic acid, l~amino-4- or -5-methoxybenzene-2-sulfonic acid, ~-amino-6-methoxybenzene-3- or -4-sulfonic acid, l-amino-6-ethoxybenzene-3- or -4-sulfonic acid, l-amino~2,4-dimethoxybenzene-6-sulfonic acid, - .~

- - ,, ;

- 2~ -l-amino-2,5-dimethoxybenzene-4 sulfonic acid, l-amino-3-acetylaminobenzene-6-sulfonic acid, l-amino-4-acetylaminobenzene-2-sulfonic acid, l-amino-3-acetylamino~4-methylbenzene-6-sulfonic acid, -aminonaphthalene-2-, -4-, -5-, -6-, -7- or -8-sulfonic acid~
2-aminonalphthalene-l-~ -5- or -6-sulfonic acid, l-aminonaphthalene-3,6- or -5,7-disulfonic acid, 2-aminonaphthalene-1,5-, -1,7-~ -3,6-, -5,7-, -4,8- or -6,8 -disulfonic acid, l-aminonaphthalene-2,5,7 trisulfonic acid, 2-aminonaphthalene-1,5,7-, -3,6,8- of 4~6~8-trisulfonic acid, l-hydroxy-2-aminobenzene-4-sulfonic acid, l-hydroxy-2-aminobenzene-S-sulfonic acid, l-hydroxy-2-aminobenzene-4,6-disulfonic acid, l-hydroxy-2-amino-~-acetylaminobenæene-6-sulfonic acid, l-hydroxy-2-amino-6-acetylaminobenzene-4-sulfonic acid, l-hydroxy-2-amino-4-chlorobenzene 5 sulfonic acid, l-hydroxy-2-amino-4-methylsulfonyl-benzene, l-amino-2-hydroxy-6-nitronaphthalene-4-sulfonic acid, 2-amino-1-hydroxynaphthalene-4,8-disulfonic acid.
Cou~ n~__omponents of the formula ~9) 2-amino-5-hydroxynaphthalene-7-sulfonic acid, 2-methyl- or -ethylamino-5-hydroxynaphthalene-7-sulfonic acid, 2-(N-acetyl-N-methylamino)-5-hydroxynaphthalene-7-sulfonic acid~
2~acetylamino-5-hydroxynaphthalene-7-sulfonic acid, 2-amino-5-hydroxynaphthalene-1,7-disulfonic acid, 2-amino-8-hydroxynaphthalene-6 sulfonic acidg 2-methyl- or -ethyIamino~8-hydroxynaphthalene-6-sulfoni.c acid~

. .
, :
.
:.
. :

2-(N-acetyl-N-methylamino~-8-hydroxynaphthalene-6 sulEonic acid, 2-acetylamino-8-hydroxynaphthalene-6-sulfonic acid, 2-amino-8-hydroxynaphthalene-3,6-disulfic acid, 2-acetylamino-8-hydroxynaphthalene-3,6-disulfonic acid, l-amino-5-hydroxynaphthalene-7-sulfonic acld, l-amino-8-hydroxynaphthalene-3,6- or -4,6-disulfonic acid~
l-acetylamino-8-hydroxynaphthalene-3,6- or -4,6-disulfonic acid~
1-(4'-aminobenæoylamino)-8-hydroxynaphthalene,3,6- or -4,6-disulfonic acid5 1-(4'-nitrobenzoylamino)-8-hydroxynaphthalene, 3,6- or -4~6-disulfonic acid, 1-(3'-aminobenzoylamino~-~-hydroxynaphthalene-3,6- or -4,6-disulfonic acid, 1-(3'-nitrobenzoylamino`-8-hydroxynaph~halene-3,6- or 4,6-disulfonic acid, 2-(4'-amino-3'-sulfophenylamino~-5-hydroxynaphthalene-7-sulfonic acid.
Suitable aminobenzenes of the formula (10~ are the same as those referred to above as aminobenzenes of the formula (7).
In the production of the preferred dyes of the formula (1), wherein D is the radical of an azo dye, es-pecially of a monoazo or disazo dye~ the diazotisation of the intermediates which contain a diazotisable amino group in usually effected by treatment with nitrous acid in an aqueous solutIon of a mineral acid a~ low temperature, and the coupling is carried out at weakly acid or neutral to weakly alkaline pH values.
The condensation of the 2,4,6~rifluoro~1,3,5-triazine with the coupling components of the formula (9)~
the azo compounds of the formula (11) and the am:inobenze-.
.. , . . ..
;: . , :

nes o the formula (10) is carried out preferably in aqueous solution or suspension, at low temperature and at a weakly acid or neutral to weakly alkaline pH value. The hydrogen fluoride which is set free during the condensation is advantageously neutralised continuously by the addition of aqueous alkali hydroxides, carbonates or bicarbonates.
If the benzene or naphthalene radical A contains a complex-forming group in the ortho-position to the azo group, for example a hydroxyl or carboxyl group, it is also possible to obtain metal complexes of the fibre-re-active azo dyes of the formula (2) by treating azo com-pounds of the formula (11)~ wherein A is a benzene or .
naphthalene radical which contains a complex-forming group ~in`the ortho-position to the azo group, with metal donors before or, if desired, also after the acylation with the 2,4,6-trifluoro-1,3,5-triazine.
Copper complexes of azo dyes of the formula (2) are of particular interest. A suitable method of metalla-tion, in addition to that described above~ is also that of dealkylating metallation and, for the production of copper complexes, oxidative coppering.
The dyes of the formula (1) are new. They are distinguished by high reactivity and produce dyeings having good wet- and lightfastness properties. It is to be particularly mentioned that dyes containing substantive chromopheric groups possess outstanding solubility whilst having good exhaust and fixation properties. This feature is surprising, as usually the solubility can only be improved by introducing additional sulfo groups into the dye molecule.
The dyes of the formula (1) are suitable for dyeing and printing a very wide variety of materials, such as silk, leather, wool, polyamide fibres and polyurethanes, 9~ii7 but especially cellulosic materials of fibrous structure, such as linen, cellulose, regenerated cellulose, and especially cotton. They are suitable both for dyeing by the exhaust method and for dyeing by the pad-dyeing process, in which the goods are impregnated with aqueous and, if desired, also withsalt containing dye solutions~
and the dyes are fixed after treatment with alkali or in the presence of alkali, with or without the application of heat.
They are also suitable for printing, in parti-cular on cotton, and also for printing nitrogen-containing fibres, for example wool, silk or blends containing wool.
It i~ advisable to rinse the dyeings and prin~s thDroughly with cold and hot water, if appropriate with the addition of an agent which acts as a dispersant and promotes the diffusion cf non-fixed dye.
In the following Examples, the parts and percen~
tages are by weight.
Example 1 45.3 parts of 2-amino-6-(4'-methoxy-2' sulfo-phenylazo)-5-hydroxynaphthalene-7-sulfonic acid (prepared by coupling diazotised l-amino-4-methoxybenzene-2-sulfonic acid to 2-amino-5-hydroxynaphthalene-7-sulfonic acid) are dissolved neutral in 600 parts of water. The solution is cooled to 0-5~C by adding ice and, at this temperature, 14.2 parts of 2,4,6-trifluoro-1,3,5-triazine are added dropwise in the course of 30 minutes while keeping the pH of the xeaction mixture at 5.5-6 by simultaneously adding sodium hydroxide solution. The reaction course is followed by chromatography. As soon as no more starting material can be detected, 12.7 parts of N ethylaminoben-zene are added. A pH of 7 is kept by continuously neutra-: " ' - ,: ' '. .

.. , . ~

- 2~ - .

lising the hydrogen fluoride set free during the reaction and raising the temperature to 20~C. When the reaction is complete, the reactive dye of the formula so3l~ OH
CH30 ~ ~ N=~

~2H5 is salted out, collected by filtration, washed and dried in vacuo. It is a red powder which dyes cotton and regene-rated cellulose in clear scarlet shades of good wet- and lightfastl7ess and good fastness to rubbing.
- Further dyes having similar properties are obtai-ned by condensing the aminoazo dyes of column 1 in Table 1 with equivalent parts of 2,4,6-trifluoro~1,3,5-triazine and immediately thereafter with the amines of column 2 in accor-dance with the particulars of this Example.

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Example 2 While cooling with ice9 28 parts of concentrated hydrochloric acid are added to a solution o~ 34.7 parts of 2-aminonaphthalene-4,8-disulfonic acid ~sodium salt) and 7 parts of sodîum nitrite in 300 parts of water, and the mixture is stirred for 30 minutes at 0-~10C. After removal o excess nitrous acid, 15 parts of 3-aminophenylurea, dissolved in 10 parts of concentrated hydrochlorid acid and 150 parts of waterare added and the coupling is brought to competion by neutralising the mixture to pH 3 to 5. The resulting aminoazo dye is salted out, collected by suction, washed and then dissolved again at pH 7 in 1400 parts of water with the addition of sodium hydroxide. A solution of 26 parts of 2,4-difluoro-6-N-ethylphenylamino-1,3,5-tria-zine in 100 parts of dio~an is then added dropwide at oD
10C and the pH is kept at 6.5 to 7 with 2N sodium hydro-xide solut.ion. When the reaction (which is followed by chro-matography) is complete, the reactive dye of the formula S03~L ~F
N=N ~ NH ~

S03H `l~HCONH2 C2~15 is salted out with sodium chloride, collected by filtration and dried, affording an orange powder which dyes cotton in reddish yellow shades of good wet- and lightfastness and good fastness to rubbing.

' 7~L

Example 3 1~.2 parts of 2,4,6-trifluoro-1,3,5 triazine are added dropwise at 0C in the course of 15 minutes to a solution o 36.3 parts of the sodium salt of 1-amino-8-hydroxynaphthalene-396-disulfonic acid in 400 parts of water while keeping a pH value of 4 to 4.5 by continually neutralising the hydrogen fluoride set free during the reaction. When the reaction is complete, 14.2 parts of4-ethylamino-l-methylbenzene are ~dded and urther condensation is carried out at the above pH while raising the tempera-ture to 20C. When the reaction (which is followed by chromatography) is complete, 30 parts of diazotised 2-aminonaphthalene-1,5-disulfonic acid, suspended in 400 parts of water, are added to the resulting solution of the dyestuff intermediate. When the coupling ;s complete at a pH of 7 to 8, the dye of the formula ,~
N-~
f H ~ N

(~ H03~1~150 U C2H5 is precipitated by adding sodium chloride, collec~ed by suction, washed and dried in vacuo. The production is a dark red powder which d~es cotton or regenerated cellulose in clear bluish red shades of good wet- and lightastness and good ~astness to rubbing.

~ 45 -Example 4 -35 3 parts of the sodium salt of l-amino-hydroxy-naphthalene-3,6-disulfon;c acid are reacted with 14.2 parts o 2,4~6-trifluoro-1,3,5-triazine in accordance with the particulars of Example 30 To the solution of the dyestuff intermediate are then added at 0~ ~o 5C 17.3 parts of diazotised l-aminobenzene-2-sulfonic acid, dissolved in 200 parts oi water, and coupling is effected in a pH range of 4 to 5. When the coupling is complete, 14.2 parts of 3-ethylamino-l-methylbenzene are added to the dyestuff solu-tion. The temperature is then raised to 20C and the pH is kept at 7 to 7.5 with 2N sodium ~arbonate solution during the ensuing condensation.. When the reaction is complete, the dye o~ the formula F

S03H ~ N -H03S 03~ C2H5 is salted out with sodium chloride, collected by suction9 washed and dried in vacuo. This dye colours cellulosic fabrics in bluish red shades which are wet~ and lightfast and fast to rubbing.

... - : .

- .
. . ~: . - ,.. ... .
., 4`6 ein~ Procedure 1 2 parts of the dye obtained ac:cording to Example 1 are dissolved in 100 parts of water while adding O.S
part of sodium m-nitrobenzenesulfonate. A co~ton fabric is impregnated with the resultin~ solution to a liquor pick up of 75% and then dried.
The fabric is then impregnatecl with a warm solu-tion of 20C which contains, per li~re , 5 g of sodium hydro-xide and 300 g of sodium chloride, and squeezed out to a pick-up of 75%. The dyeing is steamed for 30 seconds at 100 to 101C, rinsed, soaped for a quater of an hour in a 0.3% boiling solution of a non-ionic detergent, rinsed and dried Dyein~ Procedure 2 2 parts of the dye obtained according to Example 1 are dissolved in 100 parts of water. The solution is added to 1900 parts of cold water, 60 parts of sodium chlo-ride are added and 100 parts of a cotton fabric are put into this dyebath. The temperature is raised to 40C and 40 parts Of~alcined sodium carbonate and another 60 parts of sodium chloride are added after 30 minutes. The temperatu-re is kept for 30 min~tes at 40C. The dyeing is rinsed and then soaped for 15 minutes in a 0.3% boiling solution of a non-ionic detergent, rinsed and dried.

' : ,. ..., :
.

Claims (27)

What is claimed is

1. Dyes of the formula (1) wherein D is the radical of an organic dye, R1 is hydrogen or methyl, R2 is alkyl of 2 to 4 carbon atoms, and X is hydrogen or methyl.

2. Dyes according to claim 1 wherein D is the radi-cal of an azo dye.

3. Dyes according to claim 2 of the formula (2) wherein A is a benzene or naphthalene radical, m is 1 or 2, n is 0 or 1, p is 0 or 1, R is alkyl of 2 to 4 carbon atoms, and X is hydrogen or methyl, and the benzene radical B can contain as further substituents alkyl groups of 1 to 4 carbon atoms, alkoxy groups of 1 to 4 carbon atoms, acylamino groups of 1 to 6 carbon atoms, amino groups, the ureido, hydroxyl, carboxyl and sulfo group, halogen, and the radical A also nitro and sulfophenylazo which itself may be substituted by chloro and methyl.

4. Heavy metal complexes of dyes according to claim 1 to 3.

5. The dye according to claim 3 of the formula (3)

6. The dye according to claim 3 of the formula (4)

7. A process for the production of dyes of the formula (1) wherein D is the radical of an organic dye, R1 is hydrogen or methyl, which comprises condensing, in any order, 2,4,6-trifluoro-s-triazine of the formula (5), an organic dye of the formula (6), or a primary product of an organic dye of the formula (6), and an aminobenaene of the formula (7), to give a dye of the formula (1), and, if primary products are used, converting these latter into the desired end dyes of the formula (1).

8. A process according to claim 7 which comprises condensing 2,4,6-trifluoro-s-triazine of the formula (5) with an organic dye of the formula (6) and condensing the primary condensation product with an aminobenzene of the formula (7).

9. A process according to clalm 7 which comprises condensing 2,4,6-trifluoro-s-triazine of the formula (5) with an aminobenzene of the formula (7) and condensing the primary condensation product with an organic dye of the formula (6).

10. A process according to claim 7 for the produc-tion of dyes of the formula (1), wherein D is the radical of an organic dye composed of two or more components, which comprises condensing a component of a dye of the formula (6) which contains a group, a 2,4,6-trifluoro-s-tria-zine of the formula (5) and an aminobenzene of the formula (7), and, in any step of the process, reacting the conden-sation product with the other component or components, of the dye of the formula (6) to give a dye of the formula (1).

11. A process according to claim 7 wherein organic dyes of the formula (6), in which D is the radical of an azo dye, are used as starting materials, or wherein diazo components and/or coupling components which contain a -N(R1)H group are condensed with the 2,4,6-trifluoro-s-tri-azine of the formula (5), and subsequently or after the further condensation with the aminobenzene of the formula (7), the dye of the formula (1) is finally obtained by coupling with the respeetive other component of the azo dye.

12. A process according to claim 11 which comprises condensing a diazo component which contains a group with a 2,4,6-trifluoro-s-triazine of the formula (5), dia-zotising the resulting condensation product and coupling the diazonium compound to a coupling component, and reac-ting the resulting azo dye before or after the coupling, with an aminobenzene of the formula (7).

13. A process according to claim 11 which comprises condensing a coupling component which contains a group with 2,4,6-trifluoro-s-triazine o the formula (5) and coupling a diazotised diazo component to the resulting condensation product, and reacting the resulting azo dye, before or after the coupling,with an aminobenzene of the formula (7).

14. A process according to claim 11 which comprises condensing a diazo component which contains a group triazine of the formula (5), and also condensing a coupling component which contains a group with a 2,4,6-trifluoro-s-triazine of the formula (5), and diazotising the conden-sation product of the diazo component and coupling the diazonium compound to the condensation product of the coupling component and reacting the resulting azo dye, before or after the coupling, with an aminobenzene of the formula (7).

15. A process according to claim 7 which comprises condensing organic dyes of the formula (6), which contain further groups in the radical D, with a corresponding amount of the 2,4,6-trifluoro-s-triazine of the formula (5), so that two or more s-triazine radicals are introduced into the dye molecule.

16. A process according to claim 7 which comprises condensing, in any order, an organic dye of the formula (12), wherein D1 is the radical of a diazo component of the ben-zene or naphthalene series, K is the radical of a coupling component of the benzene, naphthalene or heterocyclic series, and R1 is hydro-gen or methyl, 2,4,6-trifluoro-s-triazine of the formula (5) and an aminobenzene of the formula (7), to give a dye o the formula (1).

17. A process according to claim 11 for the production of dyes of the formula (2) wherein A is a radical of the benzene or naphthalene series, m is 1 or 2, n is 0 or 1, p is 0 or 1, R is alkyl of 2 to 4 carkon atoms, and X is hydrogen or methyl, and the benzene or naphthalene radical A and the benzene radical B can contain as further substituents alkyl groups of 1 to 4 carbon atoms, alkoxy groups of atoms, amino groups, the ureido, hydroxyl, carboxyl and sulfo group, halogen, and the radical A also nitro and sulfophenylazo which itself may be substituted by chloro and methyl, which comprises reacting, in any order, a diazotised amino compound of the formula A NH2 (8) a coupling component of the formula (9) 2,4,6-trifluoro-1,3,5-triazine of the formula (5), and an aminobenzene of the formula (10) by coupling and condensation, to give a dye of the formula (1).

18. A process according to claim 17 which comprises coupling a diazotised amino compound of the formula (8) to a coupling component of the formula (9) to give an azo com-pound of the formula (11) condensing said azo compound with 2,4,6-trifluoro-s-tria-zine of the formula (5) and condensing the primary conden-sation product with an aminobenzene of the formula (10) to give an azo dye of the formula (2).

19. A process according to claim 17 which comprises condensing a coupling component of the formula (9) with 2,4,6-trifluoro-s-triazine of the formula (5), condensing the primary condensation product with an arninobenzene of the formula (10), and coupling the secondary condensation product with a diazotised amino compoud of the formula (8) to give an azo dye of the formula (2).

20. A process according to claim 17 which comprises con-densing a coupling component of the formula (9) with 2,4,6-trifluoro-s-triazine of the formula (5), coupling a diazotised amino compound of the formula (8) to the primary condensation product, and condensing the resulting azo compound with an aminobenzene of the formula (10) to give an azo dye of the formula (2).

21. A process for the production of heavy metal complexes of dyes of the formula (1) wherein the dye obtained according to claim 7, 11 or 17 is reacted with heavy metal donors.

22. A process according to claim 18 for the production of the dye of the formula (3), which comprises condensing 2-amino-6-(4'-methoxy-2'-sulfo-phenylazo)-5-hydroxynaphthalene-7-sulfonic acid with 2,4,6-trifluoro-s-triazine, and replacing a fluorine atom at the s-triazine ring by a N-ethylphenylamino group by condensation with N-ethylaminobenzene.

23. A process according to claim 18 for the production of the dye of the formula (4), which comprises condensing 1-(4'-aminobenzoylamino)-7-(2"-sulfophenylazo)-8-hydroxynaphthalene-3,6-disulfonic acid with 2,4,6-trifluoro s-triazine, and re-placing a fluorine atom at the s-triazine ring by a N-ethylphenylamino group by condensation with N-ethylaminobenzene.

24. A process for dyeing and printing which comprises the use of the dyes according to claim 1.

25. A process according to claim 24 for dyeing cellulose fibres.

26. Dyeing and printing preparations which contain a dye according to claim 1.

27. The textile material, dyed or printed according to either of claims 24 or 25.